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EP0073446A1 - Silicone rubber with retarded skin-forming properties - Google Patents

Silicone rubber with retarded skin-forming properties Download PDF

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Publication number
EP0073446A1
EP0073446A1 EP82107712A EP82107712A EP0073446A1 EP 0073446 A1 EP0073446 A1 EP 0073446A1 EP 82107712 A EP82107712 A EP 82107712A EP 82107712 A EP82107712 A EP 82107712A EP 0073446 A1 EP0073446 A1 EP 0073446A1
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EP
European Patent Office
Prior art keywords
skin
weight
silicon
compositions
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP82107712A
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German (de)
French (fr)
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EP0073446B1 (en
Inventor
Erhard Dr. Dipl.-Chem. Bosch
Ingo Dr. Dipl.-Chem. Craubner
Norman Dorsch
August Dr. Dipl.-Chem. Schiller
Oswin Dr. Dipl.-Ing. Sommer
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/901—Room temperature curable silicon-containing polymer

Definitions

  • the invention relates to compositions based on organopolysiloxane which can be stored in the absence of water and which, when water enters, crosslink to form elastomers at room temperature.
  • Organopolysiloxane compositions with such properties are known for example from DE-OS 27 37 303. They are used for coatings, as jointing or cementing compounds and the like. These masses are usually already crosslinked under the influence of atmospheric moisture. This crosslinking process usually begins on the surface of the mass with the formation of a skin and continues into the interior of the mass until the mass has been completely vulcanized.
  • the object of the invention was to find masses based on organopolysiloxane which crosslink with the entry of water to give elastomers, which on the one hand show delayed skin formation, but on the other hand vulcanize at a speed comparable to conventional masses.
  • Component c) is preferably used in amounts of 0.1% by weight to 5% by weight, based on the total weight of the composition.
  • R 1 examples include alkyl radicals, such as the methyl, ethyl, n-propyl or iso-propyl radical, and octadecyl radicals, alkenyl radicals, such as the vinyl or allyl radical, cycloaliphatic radicals, such as the cyclopentyl or cyclohexyl radical, and methylcyclohexyl or Cyclohexenyl radicals, aryl radicals, such as the phenyl radical or xenyl radicals, aralkyl radicals, such as the benzyl, the ⁇ -phenylethyl or the ⁇ -phenylpropyl radical, and alkaryl radicals, such as toluyl radicals.
  • Halogenaryl radicals such as chlorophenyl or bromophenyl radicals or cyanalkyl radicals, such as the ⁇ -cyanoethyl radical, are preferred.
  • substituted polymeric or unsubstituted polymeric radicals R 1 are those which are obtained by copolymerizing, for example, vinyl acetate, ethylene, styrene, acrylic acid, methacrylic acid, acrylic acid esters, such as n-propyl acrylate, methacrylic acid esters, such as n-butyl methacrylate, acrylonitrile or methacrylonitrile, or mixtures of the above Allow monomers to be derived with diörganopolysiloxane in the presence of radical formers.
  • condensable end groups A are hydroxyl, amino-bonded via nitrogen, oxime-bonded via oxygen, alkoxy groups with 1 to 5 carbon atoms or alkoxyalkyleneoxy groups with 1 to 5 carbon atoms, in particular hydroxyl groups.
  • the diarganopolysiloxanes mentioned according to a) of the claim can be homopolymers or copolymers. Mixtures of different diorganopolysiloxanes with condensable end groups can be used.
  • At least 50% of the number of SiC-bonded residues on the diorganopolysiloxane are methyl residues.
  • the viscosity of the diorganopolysiloxanes is expediently 100 to 500,000 mPa ⁇ s at 25 ° C.
  • Amino silanes of the general formula come as at least 3 amino groups bonded via nitrogen and / or at least 3 silicon compounds containing oxygen bonded oxime groups
  • Oxime silanes of the general formula Amine oxime silanes of the general formula as well as their partial hydrolyzates with a maximum of 10 silicon atoms.
  • a means O or 1
  • the sum of a and b is at most 3.
  • R 2 and R 3 as for R 1 .
  • Specific examples of R 2 are the methyl, ethyl, progyl, vinyl and phenyl radical.
  • R 3 are the n-butyl, sec-butyl, tert-butyl and cyclohexyl radicals.
  • Y is an RR 5 C group, where R and R 5 can each have the same meaning as R 1 or an R C group, where R stands for a divalent, optionally substituted, hydrocarbon radical.
  • the silicon compounds mentioned according to b) of the claim can be used individually or in a mixture.
  • the amount of silicon compounds according to b) is preferably matched to the amount of diorganopolysiloxane according to a) so that there are at least 3 amino groups bonded to silicon via nitrogen and / or oxime groups bonded to silicon from silicon from component b) per condensation-capable end group in the diorganopolysiloxane .
  • the component according to c) is selected from the group of mercapto-functional silanes or organopolysiloxanes. It therefore contains at least one Si-C-bonded thiol group.
  • siloxanes which can also be used according to the invention and which have at least one thiol group which is bonded via Si-C can be at least one further partial hydrolysate of the abovementioned silanes having up to 10 silicon atoms or at least one further condensation group or condensation products or. Equilibrates of the silanes mentioned or. their partial hydrolyzates with condensable groups having organopolysiloxanone with up to 2000 Si atomons.
  • the component according to a) is present in amounts of 30 to 98 wt.%, Preferably 60 to 8 0 wt.%,
  • the component according to b) in amounts of 0.2 to 15% by weight, preferably 1 to 8% by weight and
  • the component according to c) is used in amounts of 0.1 to 20% by weight, preferably 0.1 to 5% by weight.
  • the weight percentages given relate to the total weight of the mass.
  • substances which could previously also be used in the production of silicone rubbers which crosslink at room temperature can also be used in the preparation of the organopolysiloxane compositions according to the invention.
  • additives are reinforcing and non-reinforcing fillers, pigments, soluble dyes, odoriferous substances, organopolysiloxane resins, polyvinyl chloride powder, corrosion inhibitors, oxidation inhibitors, heat stabilizers, solvents, adhesion promoters, condensation catalysts, such as tin salts or organotin salts, or dicarbonic acid, dibutyldiacetate compounds, such as 3-ethoxypropylamine-1 or n-hexylamine, plasticizers, such as dimethylpolysiloxane oils unblocked with trimethylsiloxy groups or phosphoric acid esters, such as trioleyl phosphate, furthermore polyglycols and block copolymers
  • reinforcing fillers are finely divided, specific surfaces of at least 50 m 2 / g of pyrogenically produced or precipitated silicas, titanium dioxide, iron oxides, aluminum oxide, zinc oxide or optionally graphitized carbon.
  • non-reinforcing fillers are fillers with specific surfaces below 50 m 2 / g, such as quartz powder, diatomaceous earth, pebble chalk, Neuburg chalk, calcium silicate, zirconium silicate, calcium silicate or aluminum silicates including those with molecular sieve properties.
  • the fillers can be hydrophobized using the methods already known to date. Mixtures of various reinforcing and / or non-reinforcing fillers can be used.
  • the constituents can be mixed in any order per se. This mixing is preferably carried out at room temperature or at temperatures up to 150 ° C with the exclusion of water.
  • the silicone rubbers according to the invention crosslink at room temperature-r a structure under the influence of humidity.
  • the crosslinking can also, if desired, take place at lower or higher temperatures. Rapid crosslinking at temperatures up to 200 ° C is possible, especially in thin layers.
  • the crosslinking can also be carried out in the presence of amounts of water which exceed the water content of the air.
  • organopolysiloxane compositions according to the invention are particularly suitable as jointing, sealing, cementing or coating compositions.
  • compositions according to the invention are used for the production of seals in screen printing processes, wherein an engine block can serve as a substrate.
  • 70 parts by weight of a dimethylpolysiloxane each having an Si-bonded hydroxyl group and having a viscosity of 18,500 mPas in the terminal units are mixed with 21 parts by weight of a dimethylpolysiloxane oil endblocked with trimethylsiloxy groups and having a viscosity of 100 nPas and 3.5 parts by weight.
  • Parts mixed pyrogenic silicon dioxide with a specific surface area of 15 0 m 2 / g. 5.4 parts by weight of methyltris (butanone-2-oximo) silane are stirred into this mass.
  • the mixture is then mixed with 0.1 part by weight of dibutyltin diacetate and 0.3 part by weight of 3-mercantropropyltrimethoxysilane. It works in the absence of water.
  • a flowable silicone rubber composition which is stable in the absence of atmospheric moisture is obtained, which cures to form an elastomer under the influence of atmospheric moisture.
  • the time to skin formation on the surface of this mass is 50% relative. Humidity and 23 ° C 6 hours.
  • the mass to be crosslinked was also filled into aluminum dishes with a diameter of 24 mm and a depth of 18 mm in order to determine the vulcanization rate. At 50% relative air humidity and 23 C, 3.5 mm were fully vulcanized after 3 days, 5.5 mm after 7 days and 10.0 mm after 14 days.
  • Example 2 The procedure according to Example 1 is repeated, with the modification that the addition of 0.3 part by weight of 3-mercaptopropyltrimethoxysilane is omitted.
  • 83 parts by weight of a dimethylpolysiloxane with a sigebonded hydroxyl group and a viscosity of 13,500 mPa ⁇ s in the terminal units were pyrogenically produced with silane hydrophobized silicon dioxide with a specific surface area of 170 m2 / g (commercial product HDK H 2000, Wacker-Chemie) mixed.
  • silane hydrophobized silicon dioxide with a specific surface area of 170 m2 / g (commercial product HDK H 2000, Wacker-Chemie) mixed.
  • 4.9 parts by weight of methyltris (butanone-2-oximo) silane and 0.1 part by weight of dibutyltin diacetate were stirred in. It was worked in the absence of water. This resulted in a flowable mass A which was stable in storage under the exclusion of atmospheric moisture.
  • the skin formation time of the mass at 50% humidity and 23 ° C is 8 hours.
  • Example 1 The mass described in Example 1 is placed on the surface of a screen printing frame.
  • the part of the sieve not covered with a film has the shape of a seal.
  • engine blocks that serve as substrates are printed with seals made of silicone rubber in a layer thickness of 200 ⁇ m.
  • the mass can be processed by screen printing over a period of 6 hours without starting to crosslink and form skin scraps. After about 24 hours, the printed seals are vulcanized at RT and 50% relative humidity. If the printed seals are placed in a drying cabinet at 150 ° C and high relative humidity, they are vulcanized under the conditions mentioned after approx. 10 minutes.
  • Example 4 The procedure according to Example 4 is repeated, with the modification that the mass according to Comparative Example 1 is used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Materials For Medical Uses (AREA)
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Abstract

The invention relates to organopolysiloxane compositions which are stable when stored under anhydrous conditions, but when exposed to moisture cure to an elastomer containing (a) a diorganopolysiloxane having terminal condensable groups, (b) a silicon compound having 3 amino groups bonded to silicon via nitrogen and/or oxime groups bonded to silicon via oxygen per molecule and (c) a silicon compound having at least one thiol group selected from mercapto-functional silanes or siloxanes. The presence of the mercapto-functional silanes or siloxanes substantially retards the formation of skin but does not substantially extend the cure time of the organopolysiloxanes compositions. These compositions are useful in, for example, screen printing, where a long skin-over time is desired.

Description

Die Erfindung betrifft Massen auf Basis von Organopolysiloxan, die unter Ausschluß von Wasser lagerfähig sind und bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vernetzen..The invention relates to compositions based on organopolysiloxane which can be stored in the absence of water and which, when water enters, crosslink to form elastomers at room temperature.

Organopolysiloxanmassen mit derartigen Eigenschaften sind beispielsweise aus DE-OS 27 37 303 bekannt. Sie werden für Beschichtungen, als Fugen- oder Verkittungsmassen und dergleichen verwendet. Die Vernetzung dieser Massen erfolgt in der Regel bereits unter dem Einfluß von Luftfeuchtigkeit. Dieser Vernetzungsprozeß beginnt gewöhnlich an der Massenoberfläche unter Ausbildung einer Haut und setzt sich ins Innere der Masse bis zur vollständigen Durchvulkanisation der Masse fort.Organopolysiloxane compositions with such properties are known for example from DE-OS 27 37 303. They are used for coatings, as jointing or cementing compounds and the like. These masses are usually already crosslinked under the influence of atmospheric moisture. This crosslinking process usually begins on the surface of the mass with the formation of a skin and continues into the interior of the mass until the mass has been completely vulcanized.

Aufgabe der Erfindung war es, unter Zutritt von Wasser zu Elastomeren vernetzende Massen auf Basis von Organopolysiloxan aufzufinden, die einerseits verzögerte Hautbildung zeigen, andererseits jedoch mit gegenüber konventionellen Massen vergleichbarer Geschwindigkeit durchvulkanisieren.The object of the invention was to find masses based on organopolysiloxane which crosslink with the entry of water to give elastomers, which on the one hand show delayed skin formation, but on the other hand vulcanize at a speed comparable to conventional masses.

Es wurde nun gefunden, daß diese Aufgabe durch Zusatz von Mercaptanen, insbesondere durch Zusatz mercaptofunktioneller Silane bzw. Siloxane zu den genannten Massen gelöst wird.It has now been found that this object is achieved by adding mercaptans, in particular by adding mercapto-functional silanes or siloxanes to the compositions mentioned.

Gegenstand der Erfindung sind unter Ausschluß von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vernetzende Massen auf Basis von Organopolysiloxan, die zumindest

  • a) kondensationsfähige Endgruppen aufweisendes Diorganopolysiloxan,
  • b) Siliciumverbindungen, die je Molekül mindestens 3 über Stickstoff an Silicium gebundene Aminogruppen und/oder über Sauerstoff an Silicium gebundene Oximgruppen aufweisen,

enthalten une die dadurch gekennzeichnet sind, daß sie als zumindest eine weitere Komponente
  • c) Siliciumverbindungen enthalten, die je Molekül mindestens eine über Kohlenstoff gebundene Thiolgruppe aufweisen.
The invention relates to compositions which are storable with the exclusion of water and which crosslink to form elastomers when water is admitted at room temperature and which are at least based on organopolysiloxane
  • a) diorganopolysiloxane having condensable end groups,
  • b) silicon compounds which per molecule have at least 3 amino groups bonded to silicon via nitrogen and / or oxime groups bonded to silicon via oxygen,

contain une which are characterized in that they act as at least one further component
  • c) contain silicon compounds which have at least one carbon-bonded thiol group per molecule.

Die Komponente c) gemäß Anspruch wird vorzugsweise in Mengen von 0,1 Gew.% bis 5 Gew.%, bezogen auf das Gesamtgewicht der Masse eingesetzt.Component c) is preferably used in amounts of 0.1% by weight to 5% by weight, based on the total weight of the composition.

Die im Rahmen der Erfindung einzusetzenden kondensationsfähige Endgruppen aufweisenden Diorganopolysiloxane können durch die allgemeine Formel

Figure imgb0001
wiedergegeben werden, wobei

  • R 1 für gleiche oder verschiedene, einwertige, ggf. substituierte und/oder polymere Kohlenwasserstoffreste steht
  • x eine ganze Zahl im Wert von mindestens 10 ist und
  • A eine kondensationsfähige Gruppe bedeutet.
The diorganopolysiloxanes containing condensable end groups to be used in the context of the invention can be represented by the general formula
Figure imgb0001
 are reproduced, whereby
  • R 1 stands for identical or different, monovalent, optionally substituted and / or polymeric hydrocarbon radicals
  • x is an integer with a value of at least 10 and
  • A represents a condensable group.

Beispiele für R1 sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl- oder der iso-Propylrcst sowie Octadecylreste, Alkenylreste, wie der Vinyl- oder Allylrest, cycloaliphatische Reste, wie der Cyclopentyl- oder Cyclohexylrest, sowie Methylcyclohexyl- oder Cyclohexenylreste, Arylreste, wie der Phenylrest oder Xenylreste, Aralkylreste, wie der Benzyl-, der ß-Phenylethyl- oder der ß-Phenylpropylrest, sowie Alkarylreste, wie Toluylreste. Unter den substituierten Kohlenwasserstooffresten sind Halogenarylreste, wie Chlorphenyl- oder Bromphenylreste oder Cyanalkylreste, wie der β-Cyanethylrest bevorzugt.Examples of R 1 are alkyl radicals, such as the methyl, ethyl, n-propyl or iso-propyl radical, and octadecyl radicals, alkenyl radicals, such as the vinyl or allyl radical, cycloaliphatic radicals, such as the cyclopentyl or cyclohexyl radical, and methylcyclohexyl or Cyclohexenyl radicals, aryl radicals, such as the phenyl radical or xenyl radicals, aralkyl radicals, such as the benzyl, the β-phenylethyl or the β-phenylpropyl radical, and alkaryl radicals, such as toluyl radicals. Among the substituted hydrocarbon residues Halogenaryl radicals, such as chlorophenyl or bromophenyl radicals or cyanalkyl radicals, such as the β-cyanoethyl radical, are preferred.

Beispiele für substituierte polymere oder unsubstituierte polymere Reste R1 sind solche, die sich durch Copolymerisation von beispielsweise Vinylacetat, Ethylen, Styrol, Acrylsäure, Methacrylsäure, Acrylsäureester, wie n-Propylacrylat, Methacrylsäureester, wie n-Butylmethacrylat, Acrylnitril oder Methacrylnitril oder Gemischen der genannten Monomeren mit Diörganopolysiloxan in Gegenwart von Radikalbildnern herleiten lassen.Examples of substituted polymeric or unsubstituted polymeric radicals R 1 are those which are obtained by copolymerizing, for example, vinyl acetate, ethylene, styrene, acrylic acid, methacrylic acid, acrylic acid esters, such as n-propyl acrylate, methacrylic acid esters, such as n-butyl methacrylate, acrylonitrile or methacrylonitrile, or mixtures of the above Allow monomers to be derived with diörganopolysiloxane in the presence of radical formers.

Beispiele für kondensationsfähige Endgruppen A sind Hydroxyl-, über Stickstoff gebundene Amino-, über Sauerstoff gebundene Oximgruppen, Alkoxygruppen mit 1 bis 5 Kohlenstoffatomen oder Alkoxyalkylenoxygruppen mit 1 bis 5 Kohlenstoffatomen, insbesondere Hydroxylgruppen.Examples of condensable end groups A are hydroxyl, amino-bonded via nitrogen, oxime-bonded via oxygen, alkoxy groups with 1 to 5 carbon atoms or alkoxyalkyleneoxy groups with 1 to 5 carbon atoms, in particular hydroxyl groups.

Bei den genannten Diarganopolysiloxanen gemäß a) des Anspruchs kann es sich um Homo- oder Hischpolymerisate handeln. Es können Gemische aus verschiedenen, kondensationsfähige Endgruppen aufweisenden Diorganopolysiloxanen verwendet werden.The diarganopolysiloxanes mentioned according to a) of the claim can be homopolymers or copolymers. Mixtures of different diorganopolysiloxanes with condensable end groups can be used.

Vorzugsweise sind mindestens 50 % der Anzahl der SiC-gebundenen Reste am Diorganopolysiloxan Methylreste.Preferably at least 50% of the number of SiC-bonded residues on the diorganopolysiloxane are methyl residues.

Zweckmäßigerweise beträgt die Viskosität der Diorganopolysiloxane 100 bis 500.000 mPa-s bei 25 °C.The viscosity of the diorganopolysiloxanes is expediently 100 to 500,000 mPa · s at 25 ° C.

Als mindestens 3 über Stickstoff gebundene Aminogruppen und/oder mindestens 3 über Sauerstoff gebundene Oximgruppen aufweisenden Siliciumverbindungen kommen Aminosilane der allgemeinen Formel

Figure imgb0002
Oximsilane der allgemeinen Formel
Figure imgb0003
Amin-Oxim-Silane der allgemeinen Formel
Figure imgb0004
sowie deren Teilhydrolysate mit höchstens 10 Siliciumatomen in Betracht.Amino silanes of the general formula come as at least 3 amino groups bonded via nitrogen and / or at least 3 silicon compounds containing oxygen bonded oxime groups
Figure imgb0002
 Oxime silanes of the general formula
Figure imgb0003
 Amine oxime silanes of the general formula
Figure imgb0004
 as well as their partial hydrolyzates with a maximum of 10 silicon atoms.

a bedeutet in diesen allgemeinen Formeln O oder 1, die Summe aus a und b ist höchstens 3. Für R 2 und R3 gilt die selbe Definition, wie für R1. Spezielle Beispiele für R2 sind der Methyl-, Ethyl-, Progyl-, Vinyl- une Phenylrest. Spezielle Beispiele für R3 sind der n-Butyl-, sec.-Butyl-, der tert.-Butyl- und der Cyclohexylrest.In these general formulas, a means O or 1, the sum of a and b is at most 3. The same definition applies to R 2 and R 3 as for R 1 . Specific examples of R 2 are the methyl, ethyl, progyl, vinyl and phenyl radical. Specific examples of R 3 are the n-butyl, sec-butyl, tert-butyl and cyclohexyl radicals.

Y ist eine R R5 C-Grupoe, wobei R und R5 jeweils die gleiche Be- deutung wie R1 haben können oder eine R C-Gruppe, wobei R für einen zweiwertigen, ggf. substituierten, Kohlenwasserstoffrest steht.Y is an RR 5 C group, where R and R 5 can each have the same meaning as R 1 or an R C group, where R stands for a divalent, optionally substituted, hydrocarbon radical.

Spezielle Bezspiele für Siliciumverbindungen, die insgesamt mindestens 3 über Stickstoff an Silicium gebundene Aminogruppen und/oder über Sauerstoff an Silicium gebundene Oximgruppen je Molekül aufweisen, sindSpecial examples for silicon compounds which have a total of at least 3 amino groups bonded to silicon via nitrogen and / or oxime groups bonded to silicon via oxygen per molecule

Methyltris-(n-Butylamino)-Silan, Methyltris-(sec.-Butylamino)-Silan, Methyltris-(Cyclahexylamino)-Silan, Methyltris-(MethylI- ethylketoxim)-Silan, Methylbis-(Methylethylketoxim)-Cyclohexyl- aminosilan, Methyltris-(Acetonooxim)-Silan.Methyl tris (n-butylamino) silane, methyl tris (sec.-butylamino) silane, methyl tris (cyclahexylamino) silane, methyl tris (methylI-ethyl ketoxime) silane, methyl bis (methyl ethyl ketoxime) cyclohexyl aminosilane, methyl tris - (Acetonooxime) silane.

Die genannten Siliciumverbindungen gemäß b) des Anspruchs können einzeln oder im Gemisch eingesetzt werden.The silicon compounds mentioned according to b) of the claim can be used individually or in a mixture.

Die Menge an Siliciumverbindungen gemäß b) wird vorzugsweise auf die Menge an Diorganopolysiloxan gemäß a) so abgestimmt, daß pro kondensationafähiger Endgruppe im Diorganopolysiloxan mindestens 3 über Stickstoff an Silicium gebundene Aminogruppen und/oder über Sauerstoff an Silicium gebundene Oximgruppen aus der Komponente gemäß b) vorliegen.The amount of silicon compounds according to b) is preferably matched to the amount of diorganopolysiloxane according to a) so that there are at least 3 amino groups bonded to silicon via nitrogen and / or oxime groups bonded to silicon from silicon from component b) per condensation-capable end group in the diorganopolysiloxane .

Die Komponente gemäß c) ist ausgewählt aus der Gruppe der mercaptofunktionellen Silane oder -Organopolysiloxane. Sie enthält mithin mindestens eine Si-C-gebundene Thiolgruppe.The component according to c) is selected from the group of mercapto-functional silanes or organopolysiloxanes. It therefore contains at least one Si-C-bonded thiol group.

Die erfindungsgemäßen Silane lassen sich durch die allgemeine Formel

Figure imgb0005
darstellen, wobei Q eine
Figure imgb0006
darstellt und p eine ganze Zahl von 1 bis 5, vorzugsweise 3, ist.

  • R7 ist eine Alkoxygruppe mit 1 bis 5 Kohlenstoffatomen, vorzugsweise die Methoxygruppe.
  • R8 hat die gleiche Bedeutung wie R1.
  • c ist eine ganze Zahl von 1 bis 3.
  • d ist eine ganze Zahl von 0 bis 2.
  • Ferner ist die Summe von c-und d höchstens 3.
The silanes according to the invention can be represented by the general formula
Figure imgb0005
 represent, where Q is a
Figure imgb0006
 represents and p is an integer from 1 to 5, preferably 3.
  • R 7 is an alkoxy group with 1 to 5 carbon atoms, preferably the methoxy group.
  • R 8 has the same meaning as R 1 .
  • c is an integer from 1 to 3.
  • d is an integer from 0 to 2.
  • Furthermore, the sum of c and d is at most 3.

Die erfindungsgemäß ebenso einsetzbaren Siloxane, die mindestens eine über Si-C-gebundcne Thiolgruppe aufweisen, können mindestens noch eine weitere kondensationsfähige Gruppe aufweisende Teilhydrolysate der obengenannten Silane mit bis zu 10 Siliciumatomen sein oder mindestens eine weitere kondensationsfähige Gruppe aufweisende Kondensationsprodukte bzm. Äquilibrate der genannten Silane oder. deren Teilhydrolysate mit kondensationsfähige Gruppen aufweisenden Organopolysiloxanon mit bis zu 2000 Si-Atomon.The siloxanes which can also be used according to the invention and which have at least one thiol group which is bonded via Si-C can be at least one further partial hydrolysate of the abovementioned silanes having up to 10 silicon atoms or at least one further condensation group or condensation products or. Equilibrates of the silanes mentioned or. their partial hydrolyzates with condensable groups having organopolysiloxanone with up to 2000 Si atomons.

Die Komponente gemäß a) wird in Mengen von 30 bis 98 Gew.%, vorzugsweise 60 bis 80 Gew.%,The component according to a) is present in amounts of 30 to 98 wt.%, Preferably 60 to 8 0 wt.%,

die Komponente gemäß b) in Mengen von 0,2 bis 15 Gew.%, vorzugsweise 1 bis 8 Gew.% undthe component according to b) in amounts of 0.2 to 15% by weight, preferably 1 to 8% by weight and

die Komponente gemäß c) in Mengen von 0,1 bis 20 Gew.%, vorzugsweise 0,1 bis 5 Gew.%, eingesetzt.the component according to c) is used in amounts of 0.1 to 20% by weight, preferably 0.1 to 5% by weight.

Die angegebenen Gewichtsprozenteinheiten beziehen sich dabei jeweils auf das Gesamtgewicht der Masse.The weight percentages given relate to the total weight of the mass.

Zusätzlich zu den Komponenten gemäß a), b) und c) können bei der Bereitung der erfindungsgemäßen Organopolysiloxanmassen Stoffe mitverwendet werden, die auch bisher bei der Herstellung von bei Raumtemperatur vernetzenden Silikonkautschuken mitverwendet werden konnten. Beispiele für solche Zusatzstoffe sind verstärkende und nichtverstärkende Füllstoffe, Pigmente, lösliche Farbstoffe, Riechstoffe, Organopolysiloxanharze, Polyvinylchloridpulver, Korrosionsinhibitoren, Oxidationsinhibitoren, Hitzestabilisatoren, Lösungsmittel, Haftvermittler, Kondensationskatalysatoren, wie Zinnsalze oder Organozinnsalze von Carbonsäuren, wie Dibutylzinndilaurat, -diacetat, oder basische Stickstoffverbindungen, wie 3-Ethoxypropylamin-1 oder n-Hexylamin, Weichmacher, wie mit Trimethylsiloxygruppen entblockierte Dimethylpolysiloxanöle oder Phosphorsäureester, wie Trioleylphosphat, ferner Polyglykole sowie Blockmischpolymerisate von Organopolysiloxanen und Polyglykolen.In addition to the components according to a), b) and c), substances which could previously also be used in the production of silicone rubbers which crosslink at room temperature can also be used in the preparation of the organopolysiloxane compositions according to the invention. Examples of such additives are reinforcing and non-reinforcing fillers, pigments, soluble dyes, odoriferous substances, organopolysiloxane resins, polyvinyl chloride powder, corrosion inhibitors, oxidation inhibitors, heat stabilizers, solvents, adhesion promoters, condensation catalysts, such as tin salts or organotin salts, or dicarbonic acid, dibutyldiacetate compounds, such as 3-ethoxypropylamine-1 or n-hexylamine, plasticizers, such as dimethylpolysiloxane oils unblocked with trimethylsiloxy groups or phosphoric acid esters, such as trioleyl phosphate, furthermore polyglycols and block copolymers of organopolysiloxanes and polyglycols.

Beispiele für verstärkende-Füllstoffe sind feinteilige, spezifische Oberflächen von mindestens 50 m2/g aufweisende pyrogen erzeugte oder gefällte Kieselsäuren, Titandioxid, Eisenoxide, Aluminiumoxid, Zinkoxid oder ggf. graphitierter Kohlenstoff.Examples of reinforcing fillers are finely divided, specific surfaces of at least 50 m 2 / g of pyrogenically produced or precipitated silicas, titanium dioxide, iron oxides, aluminum oxide, zinc oxide or optionally graphitized carbon.

Beispiele für nichtverstärkende Füllstoffe sind Füllstoffe mit spezifischen Oberflächen unter 50 m2/g, wie beispielsweise Quarzmehl, Diatomenerde, Kieselkreide, Neuburger Kreide, Calciumsilikat, Zirkonsilikat, Calciumsilikat oder Alumosilikate einschließlich solcher mit Molekularsiebeigenschaften.Examples of non-reinforcing fillers are fillers with specific surfaces below 50 m 2 / g, such as quartz powder, diatomaceous earth, pebble chalk, Neuburg chalk, calcium silicate, zirconium silicate, calcium silicate or aluminum silicates including those with molecular sieve properties.

Die Füllstoffe können nach den auch bereits bisher bekannten Methoden hydrophobiert sein. Es können Gemische aus verschiedenen, verstärkenden und/oder nichtverstärkenden Füllstoffen eingesetzt werden.The fillers can be hydrophobized using the methods already known to date. Mixtures of various reinforcing and / or non-reinforcing fillers can be used.

Zur Herstellung der erfindungsgemäßen Silikonkautschuke können die Bestandteile in an sich beliebiger Reihenfolge vermischt werden. Dieses Vermischen erfolgt vorzugsweise bei Raumtemperatur oder bei Temperaturen bis 150 °C unter Ausschluß von Wasser.To produce the silicone rubbers according to the invention, the constituents can be mixed in any order per se. This mixing is preferably carried out at room temperature or at temperatures up to 150 ° C with the exclusion of water.

Die erfindungsgemäßen Silikonkautschuke vernetzen bei Raumtempe- ratur unter dem Einfluß der Luftfeuchtigkeit. Die Vernetzung kann aber auch, falls erwünscht, bei niedrigeren oder höheren Temperaturen erfolgen. Insbesondere in dünnen Schichten ist eine schnelle Vernetzung bei Temperaturen bis zu 200 °C möglich. Die Vernetzung kann auch in Gegenwart von den Wassergehalt der Luft übersteigenden Mengen an Wasser durchgeführt werden.The silicone rubbers according to the invention crosslink at room temperature-r a structure under the influence of humidity. The crosslinking can also, if desired, take place at lower or higher temperatures. Rapid crosslinking at temperatures up to 200 ° C is possible, especially in thin layers. The crosslinking can also be carried out in the presence of amounts of water which exceed the water content of the air.

Die erfindungsgemäßen Organopolysiloxanmassen eignen sich insbesondere als Fugen-, Dichtungs-, Verkittungs- oder Beschichtungsmassen.The organopolysiloxane compositions according to the invention are particularly suitable as jointing, sealing, cementing or coating compositions.

Der erfindungsgemäße Zusatz mercaptofunktioneller Silane bzw. Siloxane bewirkt eine extrem verlängerte Hautbildungszeit der Massen. Gleichwohl vulkanisieren die Kautschuke in vergleichbarer Geschwindigkeit. Sie werden deshalb insbesondere zur Verwendung in Siebdruckverfahren eingesetzt. Im speziellen Fall werden die erfindungsgemäßen Massen zur Hersiellmng von Dichtungen in Siebdruckverfahren eingeäetzt, wobei ein Motorblock als Substrat dienen kann.The addition of mercapto-functional silanes or siloxanes according to the invention results in an extremely prolonged skin formation time of the compositions. Nevertheless, the rubbers vulcanize at a comparable speed. They are therefore used in particular for use in screen printing processes. In a special case, the compositions according to the invention are used for the production of seals in screen printing processes, wherein an engine block can serve as a substrate.

Beispiel 1example 1

70 Gew.-Teile eines in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans einer Viskosität von 18.500 mPa·s werden mit 21 Gew.-Teilen eines mit Trimethylsiloxigruppen endblockierten Dimethylpolysiloxanöls einer Viskosität von 100 nPa·s und 3,5 Gew.-Teilen pyrogen erzeugten Siliciumdioxids mit einer spezifischen Oberfläche von 150 m2/g vermischt. In diese Masse werden 5, 4 Gew.-Teile Methyl- tris(Butanon-2-oximo)-Silan eingerührt. Danach wird die Mischung noch mit 0,1 Gew.-Teil Dibutylzinndiacetat und 0,3 Gew.-Teilen 3-Mercantonropyltrimethoxysilan versetzt. Es wird unter Ausschluß von Wasser gearbeitet.70 parts by weight of a dimethylpolysiloxane each having an Si-bonded hydroxyl group and having a viscosity of 18,500 mPas in the terminal units are mixed with 21 parts by weight of a dimethylpolysiloxane oil endblocked with trimethylsiloxy groups and having a viscosity of 100 nPas and 3.5 parts by weight. Parts mixed pyrogenic silicon dioxide with a specific surface area of 15 0 m 2 / g. 5.4 parts by weight of methyltris (butanone-2-oximo) silane are stirred into this mass. The mixture is then mixed with 0.1 part by weight of dibutyltin diacetate and 0.3 part by weight of 3-mercantropropyltrimethoxysilane. It works in the absence of water.

Es wird eine fließfähige, unter Ausschluß von Luftfeuchtigkeit lagerstabile Silikonkautschukmasse erhalten, die unter dem Einfluß von Luftfeuchtigkeit zu einem Elastomeren härtet.A flowable silicone rubber composition which is stable in the absence of atmospheric moisture is obtained, which cures to form an elastomer under the influence of atmospheric moisture.

Die Zeit bis zur Bildung einer Haut an der Oberfläche dieser Masse beträgt bei 50 %-iger relativer. Luftfeuchtigkeit und 23 °C 6 Stunden.The time to skin formation on the surface of this mass is 50% relative. Humidity and 23 ° C 6 hours.

Die zu vernetzende Masse wurde ferner in Aluminiumschälchen mit 24 mm Durchmesser und 18 mm Tiefe gefüllt um die Vulkanisationsgeschwindigkeit zu bestimmen. Bei 50 %-iger relativer Luftfeuchtigkeit und 23 C waren nach 3 Tagen 3,5 mm, nach 7 Tagen 5,5 mm und nach 14 Tagen 10,0 mm in der Tiefe durchvulkanisiert.The mass to be crosslinked was also filled into aluminum dishes with a diameter of 24 mm and a depth of 18 mm in order to determine the vulcanization rate. At 50% relative air humidity and 23 C, 3.5 mm were fully vulcanized after 3 days, 5.5 mm after 7 days and 10.0 mm after 14 days.

Vergleichsbeispiel 1Comparative Example 1

Es wird die Arbeitsweise gemäß Beispiel 1 wiederholt, mit der Abänderung, daß der Zusatz von 0,3 Gew.-Teilen 3-Mercaptopropyltrimethoxysilan unterbleibt.The procedure according to Example 1 is repeated, with the modification that the addition of 0.3 part by weight of 3-mercaptopropyltrimethoxysilane is omitted.

Die Hautbilduzgszeit der Masse, bei 50 %-iger relativer Luftfeuchtigkeit und 23 °C betrug 1 Stunde.The skin formation time of the mass, at 50% relative atmospheric humidity and 23 ° C., was 1 hour.

Vulkanisationsgeschwindigkeit:

  • Es waren bei einer 50 %-igen relativen Luftfeuchtigkeit bei 23 °C nach 3 Tagen 4,5 mm, nach 7 Tagen 6,5 mm und nach 14 Tagen 11,0 mm in der Tiefe durchvulkanisiert.
Vulcanization speed:
  • At 50% relative atmospheric humidity at 23 ° C, 4.5 mm was completely vulcanized after 3 days, 6.5 mm after 7 days and 11.0 mm after 14 days.

Beispiel 2Example 2

83 Gew.-Teile eines in den endständigen Einheiten je eine Sigebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans einer Viskosität von 13.500 mPa·s wurden mit 12 Gew.-Teilen pyrogen erzeugten, mit Silan hydrophobierten Siliciumdioxids mit einer spezifischen Oberfläche von 170 m2/g (Handelsprodukt HDK H 2000, Wacker-Chemie) vermischt. Dazu wurden 4,9 Gew.-Teile Methyltris-(butanon-2-oximo)-Silan und 0,1 Gew.-Teile Dibutylzinndiacetat eingerührt. Es wurde unter Ausschluß von Wasser gearbeitet. Dabei entstand eine fließfähige, unter Ausschluß von Luftfeuchtigkeit lagerstabile Masse A.83 parts by weight of a dimethylpolysiloxane with a sigebonded hydroxyl group and a viscosity of 13,500 mPa · s in the terminal units were pyrogenically produced with silane hydrophobized silicon dioxide with a specific surface area of 170 m2 / g (commercial product HDK H 2000, Wacker-Chemie) mixed. For this, 4.9 parts by weight of methyltris (butanone-2-oximo) silane and 0.1 part by weight of dibutyltin diacetate were stirred in. It was worked in the absence of water. This resulted in a flowable mass A which was stable in storage under the exclusion of atmospheric moisture.

In diese Masse wurden

  • a) 0,5 Gew.-Teile 3-Mercaptopropyltrinetiuoxysilan (unter Erhalt der Masse B)
  • b) 0,5 Gew.-Teile Dimethyl-3-mercaptopropylmethoxysilan (unter Erhalt der Masse C)
  • c) 1 Gew.-Teil eines Umsetzungsprodukts aus 600 g eines in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans mit 3,7 Gew.% Si-gebundenen Hydroxylgruppen und 200 g 3-Mercaptopropyltrimethoxysilans (unter Erhalt der Masse D)
  • d) 0,5 Gew.-Teile eines durchschnittlich 2 Siliciumatome enthaltenden Teilhydrolysats von 3-Mercaptopropyltrimethoxysilan (unter Erhalt der Masse E)

eingerührt.In this mass
  • a) 0.5 part by weight of 3-mercaptopropyltrinetiuoxysilan (to obtain mass B)
  • b) 0.5 part by weight of dimethyl-3-mercaptopropylmethoxysilane (to obtain mass C)
  • c) 1 part by weight of a reaction product of 600 g of a dimethylpolysiloxane each having an Si-bonded hydroxyl group in the terminal units and having 3.7% by weight of Si-bonded hydroxyl groups and 200 g of 3-mercaptopropyltrimethoxysilane (to obtain mass D)
  • d) 0.5 part by weight of a partial hydrolyzate of 3-mercaptopropyltrimethoxysilane containing an average of 2 silicon atoms (to obtain mass E)

stirred in.

In der folgenden Tabelle werden die Hautbildungszeiten der Massen bei 5 %-iger relativer Luftfeuchtigkeit und 23 °C angegeben:

Figure imgb0007
The following table shows the skin formation times of the masses at 5% relative atmospheric humidity and 23 ° C:
Figure imgb0007

Beispiel 3Example 3

83,3 Gew.-Teile eines in den endständigen Einheiten je eine Sigebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans werden mit 4,5 Gew.-Teilen Methyitris(butanon-2-oximo)-Silans und 12 Gew.-Teilen graphitierten Kohlenstoffs mit einer spezifischen Oberfläche von 70 m2/g vermischt. Dieser Mischung werden noch 0,2 Gew.-Teile Dibutylzinndilaurat und 0,3 Gew.-Teile 3-Mercaptopropyltrimethoxysilans zugesetzt.83.3 parts by weight of a dimethylpolysiloxane containing one sigebound hydroxyl group in the terminal units are mixed with 4.5 parts by weight of methyitris (butanone-2-oximo) silane and 12 parts by weight of graphitized carbon with a specific surface area of 70 m 2 / g mixed. 0.2 part by weight of dibutyltin dilaurate and 0.3 part by weight of 3-mercaptopropyltrimethoxysilane are also added to this mixture.

Es wird eine standfeste, unter Ausschluß von Luftfeuchtigkeit lagerstabile Masse erhalten.A stable mass which is stable in storage in the absence of atmospheric moisture is obtained.

Die Hautbildungszeit der Masse bei 50 %-iger Luftfeuchtigkeit und 23 °C beträgt 8 Stunden.The skin formation time of the mass at 50% humidity and 23 ° C is 8 hours.

Im Vergleich dazu beträgt die Hautbildungszeit einer im übrigen gleichen Masse ohne den Zusatz von 0,3 Teilen 3-Mercaptopropyltrimethoxysilans lediglich 60 Minuten.In comparison, the skin formation time of an otherwise equal mass without the addition of 0.3 part of 3-mercaptopropyltrimethoxysilane is only 60 minutes.

Beispielexample

Die in Beispiel 1 beschriebene Masse wird auf die Oberfläche eines Siebdruckrahmens gegeben. Der nicht mit einem Film belegte Teil des Siebes hat die Gestalt einer Dichtung. Mit Hilfe eines Rakels werden Motorblöcke, die als Substrate dienen, mit Dichtungen aus Silikonkautschuk in einer Schichtdicke von 200 u bedruckt.The mass described in Example 1 is placed on the surface of a screen printing frame. The part of the sieve not covered with a film has the shape of a seal. With the help of a doctor blade, engine blocks that serve as substrates are printed with seals made of silicone rubber in a layer thickness of 200 μm.

Die Masse läßt sich, ohne daß sie zu vernetzen beginnt und Hautfetzen bildet, über einen Zeitraum von 6 Stunden einwandfrei siebdrucktechnisch verarbeiten. Nach etwa 24 Stunden sind die gedruckten Dichtungen bei RT und 50 % relativer Luftfeuchtigkeit vulkanisiert. Werden die gedruckten Dichtungen in einem Trockenschrank bei 150 °C und hoher relativer Luftfeuchtigkeit gegeben, so sind sie unter den genannten Bedingungen nach ca. 10 Minuten vulkanisiert.The mass can be processed by screen printing over a period of 6 hours without starting to crosslink and form skin scraps. After about 24 hours, the printed seals are vulcanized at RT and 50% relative humidity. If the printed seals are placed in a drying cabinet at 150 ° C and high relative humidity, they are vulcanized under the conditions mentioned after approx. 10 minutes.

Vergleichsbeispiel 2Comparative Example 2

Es wird die Arbeitsweise gemäß Beispiel 4 wiederholt, mit der Abänderung, daß die Masse gemäß Vergleichsbeispiel 1 eingesetzt wird.The procedure according to Example 4 is repeated, with the modification that the mass according to Comparative Example 1 is used.

Innerhalb 1 Stunde bilden sich Hautfetzen, nach 1,5 Stunden ist das Sieb verklebt.Scraps of skin form within 1 hour, after 1.5 hours the sieve is glued.

Claims (2)

1. Unter Ausschluß von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur zu Elastomeren vernetzende Masse auf Basis von Organopolysiloxan, die zumindest a) kondensationsfähige Endgruppen aufweisendes Diorganopolysiloxan, b) Siliciumverbindungen, die je Molekül mindestens 3 über Stickstoff an Silicium gebundene Aminogruppen und/oder über Sauerstoff an Silicium gebundene Oximgruppen aufweisen,
enthalten, dadurch gekennzeichnet , daß sie als zumindest eine weitere Komponente c) Siliciumverbindungen enthalten, die je Molekül mindestens eine über Kohlenstoff gebundene Thiolgruppe aufweisen. 1. With the exclusion of water, a mass which is based on organopolysiloxane and which crosslink to form elastomers when water is admitted at room temperature a) diorganopolysiloxane having condensable end groups, b) silicon compounds which per molecule have at least 3 amino groups bonded to silicon via nitrogen and / or oxime groups bonded to silicon via oxygen,
included, characterized in that they act as at least one other component c) contain silicon compounds which have at least one carbon-bonded thiol group per molecule. 2. Verwendung der Masse nach Anspruch 1 im Siebdruckverfahren.2. Use of the mass according to claim 1 in the screen printing process.
EP82107712A 1981-08-25 1982-08-23 Silicone rubber with retarded skin-forming properties Expired EP0073446B1 (en)

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